Viscose spinning solution



Patented June 30, 1942 OFFICE VISCOSE SPINNING SOLUTION Elmar Profit,Berlin-Lichterfelde, Germany, as-

signor to North New York, N. Y.,

American Rayon Corporation, a corporation of Delaware No Drawing.Application August 3, 1939, Serial No. 288,170. In Germany August 6,1938 9 Claims. This invention relates to a method for improving thephysical properties of textile structures such as filaments, threads,bands, staple fibres, and the like, made of viscose.

It is an object of the invention to improve certain of the physicalproperties of viscose structures of this type, including the wet and drystrengths and the wet and dry elongations as well as the dye afiinitythereof by introducing certain chemical agents, e. g. organic sulphurcompounds into the solutions from which such artificial structures arespun and which agents are adapted to produce eiiects analogous to thosewhich impart desirable characteristics to natural products such asanimal hair, wool, and the like.

A further object of the invention is to provide a method which can bepractised with relatively low cost materials readily obtainable on alarge scale.

It is known that in organic animal products such as wool, the sulphur,especially in the keratin, -plays a very special and very unique role inthat it functions to a certain extent as a connective and intermeshingbridging bond between the principal valence chains of the proteinmolecule.

-The quantity of sulphur which is necessary for forming these bridgingbonds is relatively small and, as a rule, amounts to 2 to 4 per cent ofthe wool substance per se. It seems that the sulphur in this case is atleast partially present in the form of disulphide bridging bonds.

ably to the good physical properties possessed by organic animalproducts, such-as 'wool, etc.

In accordance with the present invention it has been found that it-isalso possible to produce an analogous effect in the case of artificialproducts such as viscose and hence to improve the physical properties ofartificial silk, staple fibres and the like made therefrom, by addingcertain sulphurcontaining compounds to the viscose. More specrfically,for example, organic compounds of a disulphide-like nature are added tothe viscose and the viscose thus charged with sulphur com,- pounds isspun into artificial threads, bands, staple fibres, and the like. Bythis means it is possible very appreciably to improve the properties ofthe structures spun or otherwise obtained therefrom compared to thosewhich are spun without the addition of such sulphur-containingcompounds. The dry strength as well as the wet strength thereof isappreciably increased, whereas the elongation values thereof are notonly not noticeably impaired but under proper conditions It is generallyassumed that such bonds contribute appreciare actually improved.Furthermore, the dye affinity of the finished product, as a rule, isalso improved. Another feature of the invention resides in the fact thatthe addition of the disulphidelike substances to the viscose also leadsto the result that the wetting capacity of the threads thus obtained isless than is customarily the case, i. e. they are less hydrophilic thannormal regenerated cellulose.

It is probable that an explanation for the improvement in the physicalproperties of the artificial structures may be predicated upon the factthat a chemical reaction occurs between the di sulphides and thecellulose, thus forming sulphur-contain'ing bridging bonds between 'themolecular chains and producing a sort of molecular intermeshing, thatis, something similar to that inherent in keratin and also allegedlyinvolved in the vulcanization of rubber.

The following have been-found to be suitable disulphide-like substancesfor theaforesaid purpose: higher aliphatic or cyclo-aliphaticdisulphides, chlorinated higher aliphatic or cycloaliphatic disulphideswhich, for example, have taken on one mol of chlorine; and higheraliphatic or cyclo-aliphatic tetrasulphides, polysulphides, and thelike. Such organic sulphur compounds are obtained, for example, byoxidation of the corresponding mercaptans and thioglycols. Exceptionallygood results have been obtained with mixtures of substances of the typeindicated, these being derived from petroleum (or the fractions thereofwhich boil above and secured .by the roundabout method of firstproducing the halogenation products and then the correspond ingmercaptans as set forth in my co-pending application Ser. No. 189,275,now U. S. Patent No. 2,231,594 of February 11, 1941, entitled Processfor producing improving'products for pelts, furs, hairs, and textiles ofall kinds, these substances furthermore being well suited for theprocess due to their exceptional cheapness and availability in adequatequantities. It is not necessary to purify or separate these substancesor mixtures, which consist, as they do, of innumerable chemicalcompounds of the most varied nature and of disulphide-likecharacter, buton the contrary, the technical (crude) mixtures may even be used withadvantage per se directly as produced. Such substances are preferablyadded to the viscose in quantities amounting to about 5 to 15 per centof the cellulose content of the viscose.

Example I and which are obtained from petroleum indirectly by way of itschlorination products and by way of the mercaptans are intimately mixedwith about 200 kg. of viscose possessing a cellulose content of about7.2 per cent, the treated viscose being then spun into artificial silkin an acid bath containing zinc sulphate or other conventional spinbaths. The physical properties of the artificial silk so obtained arebetter than those of artificial silk spun from viscose to which thedisulphide or disulphide mixture has not been added as shown by thefollowing results:

Strength Elongation Dry Wet Dry Wet Grams Grams Percent Percent Treated204 105 22. l 38. 4 Untreated 174 78 20. 9 29. 4

Example II Elongation Amount of Strength per disulphide 100 denier 5Disulphide (based on e a cellulose content) Dry Wet Dry Wet I. Petroleumdisulphides containing about 1, Percent Grams Grams mol of chlorine. i205 94 26. 4 39. Petroleum disulphides... 10 202 95 21. l 35. 6 Withoutaddition of disulphides 0 174 78 20. 9 29. 4 II. Petroleum disulphidestreated with nitric acid- 10. 3 181 i 92 19. 2 28. 7Petroleum-bis-disulphides '1 containing 2 S2 groups- 10.3 173 1 89 23. 535.8 Without addition of disulphides L 0 160 85 18.0 26.3

It is also to be notedfihat the petroleum disulphides cause a more rapidmaturing of viscose solutions.

I wish to emphasize that any organic disulphide may be used in my novelprocess provided it is capable of chemically reacting with regeneratedcellulose. Modifications of my invention y will readily be recognized bythose skilled in the art and I desire to include all modifications cominwithin the scope of the appended claims.

I claim:

l. A spinning solution for the manufacture of artificial silk comprisinga viscose solution and ,a disulphide derived from a petroleum fractionhaving a boiling point above 120 C., said disulphide forming connectiveand intermeshing bridging bonds between the principal valence chains ofthe cellulose contained in said viscose solution.

2. A spinning solution for the manufacture of artificial silk comprisinga viscose solution and above 120 C., said disulphide forming connectivefrom a petroleum fraction having a boiling point 5 about 120 C., saiddisulphide forming connective and intermeshing bridging bonds betweenthe principal valence chains of the cellulose contained in said viscosesolution, and said percentage being based upon the cellulose content ofsaid 0 viscose solution, said percentage being based upon the cellulosecontent of said viscose solution.

3. A spinning solution for the manufacture of artificial silk comprisinga viscose solution and a disulphide derived from a halogenated petroleumfraction having a boiling point above 120 C., said disulphide formingconnective and intermeshing bridging bonds between the principal valencechains of the cellulose contained in said viscose solution.

artificial silk comprising a viscose solution and a disulphide derivedfrom a chlorinated petroleum fraction having a boiling point above 120C., said disulphide forming connective and inter- 5 meshing bridgingbonds between the principal valence chains of the cellulose contained insaid viscose solution.

5. A spinning solution for the manufacture of artificial silk comprisinga viscose solution and about 5 to 15% by weight of a disulphide derivedfrom a halogenated petroleum fraction having a boiling point above 120C., said disulphide forming connective and intermeshing bridging bondsbetween the principal valence chains of the cellulose contained in saidviscose solution, and said percentage being based upon the cellulosecontent of said viscose solution.

6. A spinning solution for the manufacture of artificial silk comprisinga viscose solution and about 5 to 15% by weight of a disulphide derivedfrom a chlorinated petroleum fraction having a boiling point above 120C., said disulphide forming connective and intermeshing bridging bondsbetween the principal valence chains of the cellulose contained in saidviscose solution, and said percentage being based upon the cellulosecontent of said viscose solution.

'7. Regenerated cellulose containing a disulphide derived from apetroleum fraction having a boiling point above 120 C., said disulphideforming connective and intermeshing bridging bonds between the principalvalence chains of ,said cellulose. 8. Riegenerated cellulose containinga disulphide derived from a halogenated petroleum fraction'having aboiling point above 120 C., said disulphide forming connective andintermeshing bridging bonds between the principal valence chains of saidcellulose.

9. Regenerated cellulose containing a disulphide derived from a.chlorinated petroleum fraction having a boiling point above120 C., saiddisulphide forming connective and intermeshing bridging bonds betweenthe principal valence chains of said cellulose.

ELMAR PROFFT.

4. A spinning solution for the manufacture of I CERTIFICATE OFCORRECTION. Patent No. 8 3%. June 50, 19M.

ELMAR PROFFT It is hereby certified that error appears in the printedSpecification of the above numbered patentrequiring correction asfollows: Page sec,- ond column, line 5-, claim for "above 120 0-, Saiddisulphide forming connective" read -about 5 to 1 zan weight of edisulphide derived-,-; line 5, same claim, for "about".read --above-;and line 10-, same clainl strike out the comma 'after "solution"; andthat the said Letters Patent should be. read with this correctiontherein that the same may conform to the record of the case in thePatent Office.

Signedend sealed this 1st day of September, A. D.. 1914.

. Henry'Ven Arsdale, (Seal) Acting Commissioner of Patents.

